Professor Matt Phillips

Biography

Matthew Phillips is Professor of Applied Physics at UTS. He was appointed as Director of the Microstructural Analysis Unit in 1996 and was Associate Head (Research) of the Department of Physics and Advanced Materials since 2006 - 2011. Professor Phillips was awarded a PhD degree from UTS in experimental solid state physics in 1991 for his work on the optical properties of native point defects and transition metals in single crystal sapphire. In 1992 he received the Cowley-Moodie award from the Australian Microscopy and Microanalysis Society.

Dr Phillips has served as Deputy Director of the UTS Centre of Materials Technology (1998 to 2000) and as Research Program Leader in the Institute for Nanoscale Technology (2002 to 2008). Professor Phillips was the Foundation Director of the UTS core research strength, Materials and Technology for Energy Efficiency (2010-2012). He was a Visiting Research Fellow at the University of Sydney in 1996, a Visiting Professor at the Université de Sherbrooke, Quebec in 2005 and a Visiting Professor at the Institute of Solid State Physics at the Technical University of Berlin in 2013. Professor Phillips is currently a member of the International Advisory Board for the Thai National Nanotechnology Center (NANOTEC).

Professor Phillips' research expertise is in materials physics, particularly in the use of novel microscopy based experimental techniques to investigate the opto-electronic properties of technologically important light-emitting materials and nanostructures. ARC Field of Research: Materials Engineering, Nanotechnology and Condensed Matter Physics. Professor Phillips has presented over 30 invited conference papers at international conferences as well as over 35 seminars in overseas laboratories and has co-authored over 260 peer reviewed publications as well as over 220 conference papers.

Low Energy Electron Beam Irradiation (LEEBI) was found to quench the donor-acceptor pair (DAP) attributed to carbon (CN at 3.28 eV at 80 K) and enhances the emission of the 3.27 eV peak, which has been attributed to a free-to-bound (e,Mg0) transition at 300 K. This results in increased cathodoluminescence (CL) emission at room temperature and a decrease in CL emission at liquid nitrogen temperatures (~77 K). 2010 IEEE.

Optoelectronic devices based on InGaN have already been commercialised, however, the Indium content is limited to around 5%. With higher Indium concentration the quantum efficiency decreases, which is thought to be due to increasing inhomogeneity. In this work it is shown that the growth of InGaN on misorientated GaN substrates forces these Indium fluctuations on a nanometre scale. Temperature dependent luminescence measurements provide information about the homogeneity of the band structure. Energy selective excitation confirms the existence of localisation centres and indicates their energetic depth. Time-resolved measurements define the lifetime of localized excitons, which provides information about radiative and nonradiative processes as well as tunnelling mechanisms between the localization centres. Indium fluctuations at the nm and ?m scale are measured using cathodoluminescence (CL) and Micro Photoluminescence (?PL) respectively. 2010 IEEE.

ZnO structures grown under controlled vapour-phase transport growth conditions were characterised by electron microscopy and high-resolution cathodoluminescence techniques. Variations in the defect related emission and morphology were observed to be dependent on the distance from the source material. Annealing of grown structures under oxygen eliminated the defect emission. These experimental observations suggest that oxygen deficiency in ZnO is linked to the defect related emission, and that defect emission is strongly influenced by the oxygen gas content during vapour transport growth. 2010 IEEE.

Nanoindentation studies were conducted on a-axis oriented ZnO single crystals. The mechanical properties and deformation mechanisms were monitored and compared to previously determined data from c-axis material. Hardness and modulus values reveal that a-axis ZnO is significantly softer than c-axis material (hardness of 2 0.2 GPa), and behaves more plastically. Additionally, the influence of contact induced damage on the defect structure of a-axis material was examined using cathodoluminescence spectroscopy and monochromatic imaging to monitor the luminescence from indent sites. Deformation directly under the indent site enhanced the occurrence of red luminescence, and was attributed to a native defect in ZnO that has a higher formation energy than the defects responsible for the green and yellow visible defect bands, which were present in ZnO during growth and clustered to the indent site during annealing. 2007 Materials Research Society.

The potential use of Fe doped GaN for spintronics applications requires a complete understanding of the electronic structure of Fe in all of its charge states. To address these issues, a set of 400 mu m thick freestanding HVPE grown GaN:Fe crystals with

We present examples of ordered assemblies of organic and biological molecules on gold(111) surfaces. The first example shows how control over mono- or multilayer assemblies of 1,4-phenylenedimethanthiol can be achieved and monitored. The second example shows how monolayers on gold can be prepared using amine groups to anchor aromatic molecules to the surface. A third example shows how ordered assemblies of genetically-engineered inorganic-binding polypeptides can be formed on gold surfaces using a 3-repeat, 14 amino acid gold-binding protein (GBP1). 2006 IEEE.

The results of nucleation of InGaAs and InAs quantum dots by selective area epitaxy are presented. By pre-patterning the substrates with different (SiO2) mask dimensions the bandgap of the quantum dots can be tuned over a large range. This technique is used to demonstrate a quantum dot lase integrated with a quantum well waveguide.

The scanning electron microsope (SEM) cna be used to study and characterise a wide variety of materials used in nanoelectronic and photonic applications. Several different techniques make use of this versatile tool. These include voltage conrtast in secondary electron imaging, charge colletion for semiconductor samples and cathodoluminescnece. These techniques are important in device nanofabrication process development and nanomaterials characterisation.

The increasing application of GaN in blue and UV light emitting diodes and lasers has generated considerable interest in its optical and electrical properties. These optical devices exhibit extremely high emission efficiencies despite the presence of a very high concentration of threading dislocations (108 1010 cm-2) that act as non-radiative recombination channels. This perceived contradiction can be been explained by small (< 100 nm) carrier diffusion lengths which effectively negate the effect of the threading dislocations on the radiative recombination efficiency. These short exciton and minority carrier diffusion lengths in GaN can be explored by cathodoluminescence (CL) microscopy and spectroscopy using a SEM equipped with a Schottky field emission gun operating at 1 kV.

We present a luminescence study of as-grown GaN and GaN:Si samples by means of low voltage cathodoluminescence (CL) at low temperature. It is shown that high spatial resolution CL microscopy allows direct luminescence mapping of threading dislocations in the doped and undoped samples. Comparison of monochromatic CL images acquired near the band gap energy (free and bound excitons) and at lower energies (recombination on defects) reveal the dopant segregation around dislocations.

The cathodoluminescent and photoluminescent properties of the nanoporous silica frustules of various diatom strains and of natural diatom samples are presented. The spectra are observed to be similar to that of pure silica glass and the phenology is therefore believed to also be somewhat similar. A strong UV-blue luminescence peak is commonly observed as well as a yellow peak at 2.15 eV. For the more heavily silicified field-collected freshwater benthic samples, a strong red peak at 1.95 eV is also observed. The 2.15 eV peak is also more strongly evident for the field-collected samples. The UV-blue peak is related to common silica defect structure but cathodoluminescent microanalysis shows that this emission is highly localized in the diatom samples. 2005 Elsevier B.V. All rights reserved.

High quality x-ray mapping (XRM) has been used for over 30 years by experienced wavelength dispersive spectroscopy (WDS) operators. Manufacturers have been developing similar techniques using energy dispersive spectroscopy (EDS) over the last 20 years. This has been generally unsuccssful due to a number of problems such as poor computer specifications, cost, time to map and generally poor peak to bacjground ratios (P:B). With improvements in all the above parameters EDS mapping is now gaining in popularity.

There have been a number f new processes developed that allow the joining of very dissimilar materials such as titanium alloys, wear resistant white irons, cast irons and ceramic materials to ferrous (mild steel) and non-ferrous (aluminium) alloys. These new processes have allowed the development of more complex composite shapes to be produced. However, with any new process development, an undertsnating of the mechanism of bonding is required. through the use of x-ray mapping (XRM), chemical phase imaging as well as electron back scattered diffraction (EBSD) analsysis, very useful information on the mass transport across the interface as well as phase segregation, texture variations and phase distribution within the bond interface can be obtained. results from this investigation on a number of bonded materials are presented and the importance of XRM and EBSD in providing a better understanding of the physical and chemical processes involved in metallurgical bonding/welding of dissimilar materials discussed.

The conventional Everhart-Thornely scintillation-photomultiplier secondary electron (SE) detector cannot function at elevated pressures due to the high voltage (~ +12kV) involved in its operation. As a result, SE imaging in the variable pressure scanning electron microscope (VPSEM) has required the development of a new generation of SE detectors that operate under low vacuum conditions. To date, three different methods have been devised to measure the secondary electron (SE) emission signal in a VPSEM. Each of these approaches involves the excitation of the chamber gas by the placement of a low voltage (< +1000V) positively biased electrode in the vicinity of the specimen. A SE image can be obtained by measuring the current induced in either the positive electrode (the gaseous secondary electron detector) or the grounded stage (the ion current detector) or via a photomultiplier that detects light emission from the gas (the gas luminescence detector). In this work, the performance of each of these three low vacuum SE detector types has been compared under identical operating conditions using a Zeiss Supra 55VPSEM and FEI XL30 ESEM.

The thermal stability of ion implanted ZnO was investigated. Heavily damaged ZnO decomposes with thermal treatment. This result has significant implications for ion implants into ZnO for p-type doping, and subsequent thermal treatments for activation. 2005 IEEE.

Zinc oxide is a very attractive material for a range of optoelectronic devices including blue light-emitting diodes and laser diodes. Though n-type doping has been successfully achieved, p-type doing of ZnO is still a challenge that must be overcome before p-n junction devices can be realized. Ion implantation is widely used in the microelectronics industry for selective area doping and device isolation. Understanding damage accumulation and recrystallization processes is important for achieving selective area doping. In this study, As (potential p-type dopant) ion implantation and annealing studies were carried out. ZnO samples were implanted with high dose (1.4 1017 ions/cm2) 300 keV As ions at room temperature. Furnace annealing of samples in the range of 900C to 1200C was employed to achieve recrystallization of amorphous layers and electrical activation of the dopant. Rutherford backscattering/channeling spectrometry, transmission electron microscopy and cathodolumiescence spectroscopy were used to monitor damage accumulation and annihilation behavior in ZnO. Results of this study have significant implications for p-type doing of ZnO by ion implantation. 2005 Materials Research Society.

Zinc oxide nano-particles (25 nm) have been investigated by cathodoluminescence spectroscopy (300 nm-1700 nm) at 80 K and 300 K following thermal annealing in high purity H2/N2, N2, O2 and Ar gaseous atmospheres. The intensity of the ZnO near band edge peak was significantly increased after heat treatment in hydrogen. Conversely, thermal annealing in the other gas types decreased this emission. This effect is attributed to hydrogen passivation of competitive non-radiative defect centers, most likely bulk zinc vacancy centers. The appearance of a strong green emission centered at 2.4 eV following thermal annealing in all gas atmospheres is ascribed to the formation of bulk oxygen vacancy defects. A strong red shift of the near band edge emission with increasing beam current at 300 K is accredited to electron beam heating rather than to an increase in the carrier density. Electron beam heating is evidenced by the occurrence of a strong black body emission in the near infrared spectral region. 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular beam epitaxy-grown GaN with different Mn concentrations (5-231019 cm-3) and codoped with Si were investigated by cathodoluminescence (CL) spectroscopy and optical transmission measurements. In the GaN:Mn, an intense absorption peak at 1.414 +/- 0.002 eV was observed. This peak was attributed to an internal 5T 2? 5E transition of the deep neutral Mn3+ state since its intensity scaled with the Mn3+ concentration. The CL measurements showed that Mn-doping concentrations around 1020 cm -3 had three effects on the emission spectrum: (i) the donor bound exciton at 3.460 eV was reduced by more than one order of magnitude, (ii) the donor-acceptor-pair band at 3.27 eV was completely quenched and (iii) the yellow luminescence centered at 2.2 eV was the strongly decreased. The latter two effects were attributed to a reduced concentration of VGa. In the infrared spectral range, three broad, Mn-doping related CL emission bands centered at 1.01 0.02 eV, 1.09 0.02 eV and 1.25 0.03 eV were observed. These bands might be related to deep donor complexes, which are generated as a result of the heavy Mn-doping, rather than internal transitions at the Mn atom.

Cathodoluminescence has recently been used successfully in detecting and determining the spatial location of the amorphous phase in plasma sprayed calcium phosphate coatings. The aim of this study is to determine whether this same technique can be used to detect different carbonate substitutions in apatites. Single crystals were analysed with cathodoluminscence spectroscopy and the results indicated a change in peak shape. The substitution of carbonate into the hydroxyapatite structure creates a more well defined peak with a narrower width at half the peak height.

Zinc oxide (ZnO) nanoparticles have recently been identified as a promising candidate for advanced nanophotonics applications and quantum technologies. This work reports the formation of luminescent point defects and describes their photophysical properties. In particular, it is shown using correlative photoluminescence, cathodoluminescence, electron paramagnetic resonance (EPR), and X-ray absorption near-edge spectroscopy that green luminescence at 2.48 eV and an EPR line at g = 2.00 belong to a surface oxygen vacancy (Vo,s+) center, while a second green emission at 2.28 eV is associated with zinc vacancy (VZn) centers. It is established that radiative point defects can be excited in the visible that exhibits nanosecond lifetimes using both above bandgap and sub-bandgap 405 and 532 nm excitation. This work provides important knowledge towards employment of point defects in ZnO in nanophotonics technologies.

Single photon sources are required for a wide range of applications in quantum information science, quantum cryptography and quantum communications. However, so far majority of room temperature emitters are only excited optically, which limits their proper integration into scalable devices. In this work, we overcome this limitation and present room temperature electrically driven light emission from localized defects in zinc oxide (ZnO) nanoparticles and thin films. The devices emit at the red spectral range and show excellent rectifying behavior. The emission is stable over an extensive period of time, providing an important prerequisite for practical devices. Our results open up possibilities to build new ZnO based quantum integrated devices that incorporate solid-state single photon sources for quantum information technologies.

Room temperature single photon emitters are very important resources for photonics and emerging quantum technologies. In this work, we study single photon emission from defect centers in 20 nm zinc oxide (ZnO) nanoparticles. The emitters exhibit bright broadband fluorescence in the red spectral range centered at 640 nm with polarized excitation and emission. The studied emitters showed continuous blinking; however, bleaching can be suppressed using a polymethyl methacrylate coating. Furthermore, hydrogen termination increased the density of single photon emitters. Our results will contribute to the identification of quantum systems in ZnO. 2014 AIP Publishing LLC.

Cathodoluminescence spectra have been measured in hydrothermal and hydrogen-doped ZnO at different excitation densities and temperatures to investigate the emission efficiencies of near-band-edge (NBE), green and yellow luminescence bands. The NBE intensity depends linearly on the electron beam excitation as expected for excitonic recombination character. The intensities of the green and yellow bands are highly dependent not only on the excitation density but also on temperature. At high excitation densities ZnO exhibits dominant green emission at room temperature; the intensity of the green band can be further controlled by doping ZnO with hydrogen, which passivates green luminescence centers. Conversely at small excitation densities (< 0.1 nA) and low temperatures the visible luminescence from ZnO is predominantly yellow due to the abundance of Li in hydrothermal ZnO. The results are explained by differences in the recombination kinetics and the relative concentrations of the green and yellow centers, and illustrate that single-color emission can be achieved in ZnO by adjusting the excitation power and temperature. 2014 Published by Elsevier B.V. All rights reserved.

Native and hydrogen-plasma induced shallow traps in hydrothermally grown ZnO crystals have been investigated by charge-based deep level transient spectroscopy, photoluminescence and cathodoluminescence microanalysis. The as-grown ZnO exhibits a trap state at 23 meV, while H-doped ZnO produced by plasma doping shows two levels at 22 meV and 11 meV below the conduction band. As-grown ZnO displays the expected thermal decay of bound excitons with increasing temperature from 7 K, while we observed an anomalous behaviour of the excitonic emission in H-doped ZnO, in which its intensity increases with increasing temperature in the range 140-300 K. Based on a multitude of optical results, a qualitative model is developed which explains the Y line structural defects, which act as an electron trap with an activation energy of 11 meV, being responsible for the anomalous temperature-dependent cathodoluminescence of H-doped ZnO. 2014 IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.

We studied bulk crystals of wurtzite AlN by means of uniaxial pressure-dependent Raman measurements. As a result, we derive the phonon pressure coefficients and deformation potentials for all zone center optical phonon modes. For the A1 and E1 modes, we further experimentally determined the uniaxial pressure dependence of their longitudinal optical-transverse optical (LO-TO) splittings. Our experimental approach delivers new insight into the large variance among previously reported phonon deformation potentials, which are predominantly based on heteroepitaxial growth of AlN and the ball-on-ring technique. Additionally, the measured phonon pressure coefficients are compared to their theoretical counterparts obtained by density functional theory implemented in the siesta package. Generally, we observe a good agreement between the calculated and measured phonon pressure coefficients but some particular Raman modes exhibit significant discrepancies similar to the case of wurtzite GaN and ZnO, clearly motivating the presented uniaxial pressure-dependent Raman measurements on bulk AlN crystals.

The influence of deep level surface defects on electrical and gas sensing properties of ZnO nanorods NH3(g) sensors was studied. ZnO nanorods 50-60 nm in diameter were synthesized via low-temperature hydrothermal growth at 90C on sapphire substrates. The as-grown nanorods exhibited a cathodoluminescence (CL) peak centered at 1.90 eV (YL), attributed to LiZn deep acceptors or O interstitials. Subsequent annealing in O2 at 1 atm and Zn vapor at 650C produced broad CL peaks centered at 1.70 eV (RL) and 2.44 eV (GL), respectively. The RL and GL have been ascribed to acceptor-like VZn and donor-like VO related centers, respectively. Electrical and gas sensing measurements established that the NH3 gas response sensitivity was 22.6 for O2 anneal (RL), 1.4 for Zn vapor anneal (GL), and 4.1 for the as-grown (YL) samples. Additionally, treatment in H-plasma quenched the RL and inverted the NH3 electrical response due to the incorporation of H donors. Changes in the gas sensing response are explained by a shift in the position of the ZnO Fermi level relative to the chemical potential of NH3 gas due to the creation of near surface donor or acceptors. These data confirm that ZnO nanorods arrays can be tailored to detect specific gas species. (Chemical Equation Presented).

The evolution of luminescence properties and voids formation with respect to annealing temperature in H implanted ZnO was investigated by depth-resolved cathodoluminescence spectroscopy (DRCLS), transmission electron microscopy and secondary ion mass spectrometry (SIMS). The annealing temperature is found to induce noticeable changes to the shape, size and empty volume density of the cavities. DRCLS results also reveal that the green emission is influenced by different annealing temperatures. In particular, the 600 C anneal produces a strong quenching of the green emission in the implanted region, while after the 800 C anneal a significant enhancement near the surface is observed. The annealing at 600 C also results in an uncommon violet emission at ?3.1 eV that is not observed after a higher annealing temperature. A clear correlation between the violet emission, vacancies and Li is revealed from comparison between the DRCLS intensities and SIMS data. 2014 IOP Publishing Ltd.

In these experiments plasma immersion ion implantation is utilised to simulate some of the radiation effects in a nuclear reactor environment. Scanning electron microscopy using the angular selective backscatter detector has revealed observable changes in crystallographic contrast after irradiation with helium ions. Further studies using electron backscatter diffraction in both plan and cross section view allow us to visualize the extent and depth of damage and observe differences in the behavior of different crystalline phases present in several grades of stainless steel. 2012 Elsevier B.V. All rights reserved.

Aligned nitrogen-doped ZnO nanowires were grown by chemical vapour deposition using Au catalyst. N incorporation was achieved through the introduction of N2O gas as a dopant source and confirmed by Raman spectroscopy, which reveals additional N-related modes at 275, 580 and 642 cm-1. The nanowires have a hexagonal faceted shape and are predominantly grown along the [001] direction. The nanowire morphology is unaffected by N incorporation. The luminescence peak at 3.24 eV was monitored as a function of N2O content. Intensity analysis of this band reveals that it can be partly attributed to donor-acceptor pair (DAP) emission originating from the N doping. 2013 Elsevier B.V. All rights reserved.

We report a new mechanism that limits the rate of electron beam induced etching (EBIE). Typically, the etch rate is assumed to scale directly with the precursor adsorbate dissociation rate. Here, we show that this is a special case, and that the rate can instead be limited by the concentration of active sites at the surface. Novel etch kinetics are expected if surface sites are activated during EBIE, and observed experimentally using the electron sensitive material ultra nanocrystalline diamond (UNCD). In practice, etch kinetics are of interest because they affect resolution, throughput, proximity effects, and the topography of nanostructures and nanostructured devices fabricated by EBIE. 2013 American Chemical Society.

The uniaxial stress dependence of the band structure and the exciton-polariton transitions in wurtzite ZnO is thoroughly studied using modern first-principles calculations based on the HSE+G0W0 approach, kp modeling using the deformation potential framework, and polarized photoluminescence measurements. The ordering of the valence bands [A(?7), B(?9), C(?7)] is found to be robust even for high uniaxial and biaxial strains. Theoretical results for the uniaxial pressure coefficients and splitting rates of the A, B, and C valence bands and their optical transitions are obtained including the effects of the spin-orbit interaction. The excitonic deformation potentials are derived and the stress rates for hydrostatic pressure are determined based on the results for uniaxial and biaxial stress. In addition, the theory for the stress dependence of the exchange interaction and longitudinal-transversal splitting of the exciton polaritons is developed using the basic exciton functions of the quasicubic approximation and taking the interaction between all exciton states into account. It is shown that the consideration of these effects is crucial for an accurate description of the stress dependence of the optical spectra in ZnO. The theoretical results are compared to polarized photoluminescence measurements of different ZnO substrates as function of uniaxial pressure and experimental values reported in the literature demonstrating an excellent agreement with the computed pressure coefficients. 2013 American Physical Society.

We studied the structural and optical properties of state-of-the-art non-polar bulk GaN grown by the ammonothermal method. The investigated samples have an extremely low dislocation density (DD) of less than 5 104?cm?2, which results in very narrow high-resolution x-ray rocking curves. The a and c lattice parameters of these stress-free GaN samples were precisely determined by using an x-ray diffraction technique based on the modified Bond method. The obtained values are compared to the lattice parameters of free-standing GaN from different methods and sources. The observed differences are discussed in terms of free-electron concentrations, point defects, and DD. Micro Raman spectroscopy revealed a very narrow phonon linewidth and negligible built-in strain in accordance with the high-resolution x-ray diffraction data. The optical transitions were investigated by cathodoluminescence measurements. The analysis of the experimental data clearly demonstrates the excellent crystalline perfection of ammonothermal GaN material and its potential for fabrication of non-polar substrates for homoepitaxial growth of GaN based device structures.

The structural and optical properties of cobalt-doped zinc oxide (Co-doped ZnO) nanoparticles have been investigated. The nanopowder with Co concentrations up to 5 at% was synthesized by a coprecipitation method. The physical structure and the chemical states of the Co-doped ZnO were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV-Visible reflectance and cathodoluminescence (CL) spectroscopy. The results show that cobalt ions predominantly occupy Zn2+ sites in the wurtzite crystal lattice and possess a valence state of 2+. CL analysis revealed that the incorporation of Co2+ creates a new emission band at 1.85 eV, but quenched the near-band-edge luminescence. Springer Science+Business Media 2013.

The crystallographic and optical properties of Mn-doped ZnO nanoparticles prepared by a sol-gel process have been investigated by X-ray diffraction, UV-visible absorption spectroscopy and cathodoluminescence microanalysis. X-ray diffraction reveals that the nanoparticles have hexagonal wurtzite crystal structure, with the lattice constants along the a- and c-axes increasing with increasing Mn concentration from 0 to 2.4 at%. For all Mn concentrations in this range, the nanoparticles are essentially free of native point defects so that they exhibit only band-edge luminescence. The optical bandgap and band-edge emission energies for Mn-doped ZnO were found to increase in proportion to the lattice constants. The direct correlation between the bandgap and crystal structure suggests that the band-edge optical properties of Mn-doped ZnO is predominantly influenced by the amount of Mn atoms substituting Zn on the lattice sites. 2012 Elsevier B.V. All rights reserved.

The doping properties and stability of hydrogen in zinc oxide (ZnO) crystals have been investigated by cathodoluminescence (CL) spectroscopy. Hydrogen incorporation was achieved by hydrogen plasma at 200 C. The ZnO near-band-edge (NBE) peak is dramatically enhanced, while the green emission at 2.4 eV is quenched with increasing hydrogen incorporation. These effects are attributed to hydrogen passivating green luminescence centers, which are most likely negatively charged zinc vacancy defects. E-beam irradiation of H-doped ZnO crystals by an intense electron beam with ?W power reverses the hydrogen doping process. This effect is ascribed to the dissociation of H-related defects, formation of Chidden H2, and electromigration of H + under the influence of the local trapped charge-induced electric field. These results highlight the potential to modify the local luminescent properties of ZnO by e-beam irradiation. 2012 Materials Research Society.

Cathodoluminescence spectra have been measured to determine the characteristics of ubiquitous green luminescence (GL) in nonstoichiometric zinc oxide (ZnO). Zn- and O-rich ZnO were found to exhibit characteristic emissions at 2.53 eV [full width at half-maximum (FWHM) 340 meV] and 2.30 eV (FWHM 450 meV), respectively. Hydrogen was used to probe the physical nature of GL centers. The Zn-rich GL is enhanced upon H incorporation, whereas the O-rich GL is completely quenched as its underlying acceptor-like V Zn centers are passivated by H. The GL emission bands each exhibit remarkably different excitation-power dependencies. The Zn-rich GL follows a close to linear relationship with excitation power, while the O-rich GL exhibits a square-root dependence. Calculations based on bimolecular recombination equations show the defect concentration in Zn-rich ZnO is three orders of magnitude greater than that in O-rich ZnO, indicating V O is more readily formed than V Zn in thermochemical treatments of ZnO. 2012 American Physical Society.

Electron beam induced deposition (EBID) is limited by low throughput and purity of as-grown material. Co-injection of O2 with the growth precursor is known to increase both the purity and deposition rate of materials such as SiO2 at room temperature. Here, we show that O2 inhibits rather than enhances EBID from tetraethoxysilane (TEOS) precursor at elevated temperatures. This behavior is attributed to surface site competition between chemisorbates at elevated temperature, and TEOS decomposition by atomic oxygen produced through electron dissociation of physisorbed O2 at room temperature. 2012 American Institute of Physics.

Models of adsorbate dissociation by energetic electrons are generalized to account for activated sticking and chemisorption, and used to simulate the rate kinetics of electron beam induced chemical vapor deposition (EBID). The model predicts a novel temperature dependence caused by thermal transitions from physisorbed to chemisorbed states that govern adsorbate coverage and EBID rates at elevated temperatures. We verify these results by experiments that also show how EBID can be used to deposit high purity materials and characterize the rates and energy barriers that govern adsorption. 2012 American Physical Society.

We report the use of ammonia (NH 3) vapor as a new precursor for nanoscale electron beam induced etching (EBIE) of carbon, and an efficient imaging medium for environmental scanning electron microscopy (ESEM). Etching is demonstrated using amorphous carbonaceous nanowires grown by electron beam induced deposition (EBID). It is ascribed to carbon volatilization by hydrogen radicals generated by electron dissociation of NH 3 adsorbates. The volatilization process is also effective at preventing the buildup of residual hydrocarbon impurities that often compromise EBIE, EBID and electron imaging. We also show that ammonia is a more efficient electron imaging medium than H 2O, which up to now has been the most commonly used ESEM imaging gas. 2012 IOP Publishing Ltd.

The self-organized growth of crystalline silicon nanodots and their structural characteristics are investigated. For the nanodot synthesis, thin amorphous silicon (a-Si) layers with different thicknesses have been deposited onto the ultrathin (2 nm) oxidized (111) surface of Si wafers by electron beam evaporation under ultrahigh vacuum conditions. The solid phase crystallization of the initial layer is induced by a subsequent in situ annealing step at 700C, which leads to the dewetting of the initial a-Si layer. This process results in the self-organized formation of highly crystalline Si nanodot islands. Scanning electron microscopy confirms that size, shape, and planar distribution of the nanodots depend on the thickness of the initial a-Si layer. Cross-sectional investigations reveal a single-crystalline structure of the nanodots. This characteristic is observed as long as the thickness of the initial a-Si layer remains under a certain threshold triggering coalescence. The underlying ultra-thin oxide is not structurally affected by the dewetting process. Furthermore, a method for the fabrication of close-packed stacks of nanodots is presented, in which each nanodot is covered by a 2 nm thick SiO 2 shell. The chemical composition of these ensembles exhibits an abrupt Si/SiO 2 interface with a low amount of suboxides. A minority charge carrier lifetime of 18 ?s inside of the nanodots is determined. 2012 Springer-Verlag.

We report the phonon deformation potentials of wurtzite GaN and ZnO for all zone center optical phonon modes determined by Raman measurements as a function of uniaxial pressure. Despite all the structural and optical similarities between these two material systems, the pressure dependency of their vibrational spectra exhibits fundamental distinctions, which is attributed to their different bond ionicities. In addition, the LO-TO splitting of the A1 and E1 phonon modes is analyzed which yields insight into the uniaxial pressure dependency of Born's transverse effective charge e T*. 2011 American Institute of Physics.

ZnO single crystals, epilayers, and nanostructures often exhibit a variety of narrow emission lines in the spectral range between 3.33 and 3.35 eV which are commonly attributed to deeply bound excitons (Y lines). In this work, we present a comprehensive study of the properties of the deeply bound excitons with particular focus on the Y0 transition at 3.333 eV. The electronic and optical properties of these centers are compared to those of the shallow impurity related exciton binding centers (I lines). In contrast to the shallow donors in ZnO, the deeply bound exciton complexes exhibit a large discrepancy between the thermal activation energy and localization energy of the excitons and cannot be described by an effective mass approach. The different properties between the shallow and deeply bound excitons are also reflected by an exceptionally small coupling of the deep centers to the lattice phonons and a small splitting between their two electron satellite transitions. Based on a multitude of different experimental results including magnetophotoluminescence, magnetoabsorption, excitation spectroscopy (PLE), time resolved photoluminescence (TRPL), and uniaxial pressure measurements, a qualitative defect model is developed which explains all Y lines as radiative recombinations of excitons bound to extended structural defect complexes. These defect complexes introduce additional donor states in ZnO. Furthermore, the spatially localized character of the defect centers is visualized in contrast to the homogeneous distribution of shallow impurity centers by monochromatic cathodoluminescence imaging. A possible relation between the defect bound excitons and the green luminescence band in ZnO is discussed. The optical properties of the defect transitions are compared to similar luminescence lines related to defect and dislocation bound excitons in other II-VI and III-V semiconductors. 2011 American Physical Society.

We report on an oxide-assisted growth technique for silica nanowires which allows tuning the growth from surface-matched nanowires to free-standing morphologies based on growth control by Ti in the role of a catalyst and surfactant. Using an adjustable Ti concentration, we grew silica nanowires with lengths ranging from 100nm up to several millimetres whose defect chemistry was analysed by electron microscopy tools, monochromatic cathodoluminescence imaging and time resolved photoluminescence spectroscopy. The knowledge of the luminescence properties and the related defect occurrence along with their spatial distribution is pivotal for advancing silica nanowire growth in order to realize successful device designs based on self-assembled Si/SiOx nanostructures. We demonstrate a core-shell structure of the grown nanowires with a highly luminescent 150nm thick shell and outstandingly fast decaying dynamics (?1ns) for glass-like materials. The conjunction of the observed efficient and stable luminescences with their attributed decaying behaviours suggests applications for silica nanowires such as active and passive optical interconnectors and white light phosphors. The identification of a time domain difference for the spectral regime from 2.3 to 3.3eV, within the confined spatial dimensions of a single nanowire, is very promising for future, e.g.data transmission applications, employing silica nanowires which exhibit achievable compatibility with commonly applied silicon-based electronics. A qualitative growth model based on silica particle diffusion and Ti-assisted seed formation is developed for the various types of segregated silica nanowires which extends commonly assumed oxide-assisted growth mechanisms. IOP Publishing Ltd.

ZnO crystals have been investigated by scanning cathodoluminescence microscopy and spectroscopy at 80 K following hydrogen incorporation by plasma exposure. The intensity of the ZnO near-band-edge (NBE) emission is greatly enhanced while the defect-related green emission is quenched following plasma treatment. These effects are attributed to the passivation of zinc vacancies by hydrogen. The green and yellow intensities and their intensity ratios to the NBE vary with excitation depth for both undoped and H-doped ZnO crystals. The intensities of the green and yellow emissions exhibit sublinear dependencies on electron beam excitation density while the NBE intensity increases linearly with the excitation density. These saturation effects with increasing excitation density must be taken into account when assessing defects in ZnO by luminescence characterization. Copyright Materials Research Society 2011.

We report on the electrical and structural properties of boron-doped diamond tips commonly used for in-situ electromechanical testing during nanoindentation. The boron dopant environment, as evidenced by cathodoluminescence (CL) microscopy, revealed significantly different boron states within each tip. Characteristic emission bands of both electrically activated and nonelectrically activated boron centers were identified in all boron-doped tips. Surface CL mapping also revealed vastly different surface properties, confirming a high amount of nonelectrically activated boron clusters at the tip surface. Raman microspectroscopy analysis showed that structural characteristics at the atomic scale for boron-doped tips also differ significantly when compared to an undoped diamond tip. Furthermore, the active boron concentration, as inferred via the Raman analysis, varied greatly from tip-to-tip. It was found that tips (or tip areas) with low overall boron concentration have a higher number of electrically inactive boron, and thus non-Ohmic contacts were made when these tips contacted metallic substrates. Conversely, tips that have higher boron concentrations and a higher number of electrically active boron centers display Ohmic-like contacts. Our results demonstrate the necessity to understand and fully characterize the boron environments, boron concentrations, and atomic structure of the tips prior to performing in situ electromechanical experiments, particularly if quantitative electrical data are required.

We demonstrate the ability of a combined scanning electron microscope and cathodoluminescence (CL) spectral mapping system to provide important spatially resolved information. The degree of inhomogeneity in spectral output across a multi-quantum well sample is measured using the SEM-CL system as well as measuring the efficiency roll-off with increasing carrier concentration. The effects of low energy electron beam modification on the InGaN/GaN multi quantum wells have also been characterized.

ZnO structures were synthesised on the sapphire (112?0) substrate by a vapour transport method in a gas flowing furnace. The influence of the oxygen content in the gas mixture on the morphology and luminescent properties of ZnO structures grown on a strip-like substrate was investigated, with all other growth parameters being kept nominally identical. Integrated electron microscopy and cathodoluminescence analysis shows gradual variations of structural and optical emission properties for ZnO structures grown on the long substrate. Defect-related green luminescence of ZnO is found to be highly dependent on the oxygen vapour in the growth region of the furnace. Our findings demonstrate that the green luminescence is associated with oxygen deficiency in ZnO. 2009 Elsevier B.V. All rights reserved.

The discoloring interaction between the artist's pigments cadmium yellow and the copper-containing malachite, an interaction that is conjectured to cause black spotting in oil paintings of the 19th and early 20th centuries, was examined using X-ray mapping and scatter diagram analysis. The application of these coupled techniques confirmed that copper sulfide phases were produced during discoloration reaction. Scatter diagram analysis indicated that two copper sulfide stoichiometries (CuS and Cu3S2) were present as reaction products where previously only crystalline CuS (covellite) had been identified by X-ray diffraction. The results demonstrate the potential of X-ray mapping coupled with scatter diagram analysis for the identification of both crystalline and X-ray amorphous phases produced by such complex heterogeneous interactions and their applicability to the investigation of interactions of artists' pigments. Microscopy Society of America 2010.

The synthesis of hexagonal ring-shaped structures of zinc oxide using nanosphere lithography and metal/metal oxide sputtering is demonstrated. This synthesis exploits the surface re-emission of zinc oxide to deposit material in regions lying out of the line-of-sight of the sputtering source. These rings can nucleate the hydrothermal growth of zinc oxide crystals. Control over the growth could be exercised by varying growth solution concentration or temperature or by applying an external potential. 2010 American Chemical Society.

Fe-doped ZnO was successfully fabricated by thermal in-diffusion of Fe into ZnO crystals. X-ray absorption near edge structure (XANES), photoemission and cathodoluminescence (CL) spectroscopy have been combined to examine the Fe diffusion and its effects on the electronic and optical properties of the crystal. Depth-resolved CL demonstrates that Fe in-diffusion occurs to at least 4 ?m depth and results in intense green luminescence, whereas the undoped crystal exhibits only the ZnO near-band-edge emission. XANES and valence-band photoemission show that Fe is incorporated as Fe2+/3+ ions on substitutional Zn sites. The results suggest that the variation in the CL properties is due to a change in the oxygen vacancy charge state as a result of electron transfer from Fe. Crown Copyright 2009.

Annealing tin doped indium oxide (ITO) thin films by self-heating shows potential for reducing the crystallization temperature required to optimize the optical and electrical properties of the films. It also shows promise as a cost effective method of studying the heat treatment process in situ. A computer based solution was developed to allow for a precise control over the annealing process. To anneal at a fixed temperature, a feedback loop senses changes in the resistance of the sample and adjusts the current across the load accordingly to ensure constant delivery of power to an ITO film. 2008 American Institute of Physics.

The surface electronic structure of ZnO nanoparticles has been studied with photoemission and x-ray absorption spectroscopies. Contrary to expectation, ZnO:Zn phosphor nanoparticles were found to contain a lower oxygen vacancy density on the surface than undoped ZnO counterparts, but oxygen vacancies are in different chemical environments. Cathodoluminescence shows intense green luminescence from the ZnO:Zn surface, while the undoped nanoparticles exhibit only the near-band-edge emission. The results indicate the roles of surface oxygen vacancies and their environment in the previously unexplained green luminescence from the ZnO:Zn material. 2008 American Institute of Physics.

Luminescence properties of vertically aligned, crystalline ZnO nanorods are studied by cathodoluminescence (CL) spectroscopy and microscopy. Results show that luminescence characteristics vary dramatically with location on the nanorod as well as CL excitation depth. CL inhomogeneity is observed between the nanorod tip and sidewalls, accompanied by a variation in the chemical environment of surface oxygen ions as probed by photoemission spectroscopy. Our findings demonstrate that CL can provide useful information on the local optical properties of nanostructured materials, which is simply beyond the capability of other methods. 2008 American Institute of Physics.

The bandwidth and contrast of secondary electron (SE) images obtained using variable pressure scanning electron microscopy are enhanced when a grounded Frisch grid is placed between the SE detecting anode and the negatively biased stage. The improvement in SE image quality occurs as a consequence of the grounded Frisch grid electrostatically screening the 'slow' induced ion current signal, generated below the grid, from the induced current detected above the grid by the anode. Ion induced artefacts, such as image smearing at fast scan rates, are virtually eliminated using a Frisch grid. Gas amplification data are presented to illustrate that gas gain can be optimized by varying the Frisch grid-stage (amplification region) separation Frisch grid-anode (drift region) separation and stage bias. 2008 IOP Publishing Ltd.

"Natural" lithography was used to prepare arrays of nanoscale capacitors on silicon. The capacitance was verified by a novel technique based on the interaction of a charged substrate with the electron beam of a scanning electron microscope. The "nanocapacitors" possessed a capacitance of ?1 10-16F and were observed to hold charge for over an hour. Our results indicate that fabricating nanostructures using natural lithography may provide a viable alternative for future nanoelectronic devices. 2008 American Chemical Society.

X-ray mapping with Silicon Drift detectors (SDDs) and multi-EDS detector systems has become an invaluable analysis technique because the time to perform an x-ray map is reduced considerably. Live x-ray imaging can now been performed with so much data collected in a matter of minutes. The use of multi-EDS detector systems has made this form of mapping even quicker and has also given users the ability to map minor and trace elements very accurately. How the data is collected and summed with multi-EDS detectors is very critical for accurate quantitative x-ray mapping (QXRM).

The near band edge emissions of an individual ZnO nanobelt were investigated by cathodoluminescence spectroscopy, which has unique advantages in higher spatial resolution, orientation, and environmental independence over the conventional photoluminescence spectroscopy. The results show that the presence of a large surface-to-volume ratio is the determinant to suppress the formation of excitons in ZnO nanobelts. Ab initio calculations show that a drastic decrease of density-of-state in the conduction band and increase in the valence band upon size reduction are the key consequence of the large surface-to-volume ratio, revealing the possible fundamental physical origin of exciton suppression. The weak exciton polarity also reduces the likelihood for an exciton to couple with longitudinal phonons. This causes a reduction in the first longitudinal phonon replica intensity and then a complete suppression of the second replica. Understanding the effect of large surface ratio upon the physical properties of ZnO nanomaterials may provide new insights into the fundamental science of nanotechnology for the development of optoelectronics. 2008 American Chemical Society.

Background: Conjugated polymers, especially those of the poly(phenylene vinylene) (PPV) family, are promising candidates as emission material in light-emitting devices. The aim of this work was to investigate the dependence of the luminescence properties of PPV-based derivatives on their polymer structure, especially side groups. Results: Three PPV derivatives, BEHPPV, MEHPPV and MEHSPPV, were synthesised and characterised by photoluminescence (PL) and cathodoluminescence (CL) spectroscopies in the temperature range 10-300K. PL and CL spectra of the polymers exhibit similar luminescence peaks, which undergo a blue shift with increasing temperature. The shift in wavelength is accompanied by variations in the relative intensities of emission peaks. Both BEHPPV and MEHPPV display emission characteristics of the PPV backbone, but the peak of MEHPPV shifts to a longer wavelength in comparison with the corresponding peak of BEHPPV at the same temperature. The luminescence spectra of MEHSPPV, which has a sulfanyl incorporated in the side chain, are considerably different from those of the two other derivatives. Conclusions: The results demonstrate that the luminescence properties depend strongly on the chain conformations of the conjugated backbone, which are affected by polymer side chains. 2007 Society of Chemical Industry.

Vertically aligned ZnO nanowires were synthesized on a sapphire (1120) substrate by vapour deposition and their light-emitting properties were characterized using photoluminescence and cathodoluminescence spectroscopies. Besides the nanowires, there exists a mosaic ZnO film on the substrate surface. Comparison of the luminescent properties of the as-grown ensemble and the nanowires extracted from it shows that the mosaic film is the major source of the defect-related green emission while the nanowires possess highly crystalline quality with virtually no defects. Photoemission spectroscopy shows that the valence band states associated with O 2p from the as-grown sample are diminished compared with those from the extracted nanowires. These findings suggest that the green emission partly arises from oxygen vacancies located on the surface of the mosaic film. IOP Publishing Ltd.

Luminescence properties of nanocomposites consisting of ZnO nanoparticles in a conjugated polymer, poly [2-methoxy-5-(2?-ethyl hexyloxy)-phenylene vinylene] (MEH-PPV), were investigated. Photoluminescence measurements reveal a blue shift in the emission spectrum of MEH-PPV upon incorporation of ZnO nanoparticles into the polymer film while the emission is increasingly quenched with increasing ZnO concentration. In contrast, the structure of the polymer and its conjugation length are not affected by the presence of ZnO nanoparticles (up to 16 wt% ZnO) as revealed by Raman spectroscopy. The blue shift and photoluminescence quenching are explained by the separation of photogenerated electron-hole pairs at the MEH-PPV/ZnO interface and the charging of the nanoparticles. Crown Copyright 2008.

We present the results of cathodoluminescence experiments on a set of Fe doped GaN samples with Fe concentrations of 5 1017, 1 1018, 1 1019, and 2 1020 cm -3. These specimens were grown by hydride vapor phase epitaxy with different concentrations of Fe. The introduction of Fe is found to promote the formation of structurally inhomogeneous regions of increased donor concentration. We detect a tendency of these regions to form hexagonal pits at the surface. The locally increased carrier concentration leads to enhanced emission from the band edge and the internal T41 (G) - A61 (S) transition of Fe3+. In these areas, the luminescence forms a finely structured highly symmetric pattern, which is attributed to defect migration along strain-field lines. Fe doping is found to quench the yellow defect luminescence band and to enhance the blue luminescence band due to the lowering of the Fermi level and the formation of point defects, respectively. 2008 American Institute of Physics.

Electron beam induced deposition (EBID) is a maskless nanofabrication technique capable of surpassing the resolution limits of resist-based lithography. However, EBID fabrication of functional nanostructures is limited by beam spread in bulk substrates, substrate charging, and delocalized film growth around deposits. Here, we overcome these problems by using environmental scanning electron microscopy (ESEM) to perform EBID and etching while eliminating charging artifacts at the nanoscale. Nanostructure morphology is tailored by slimming of deposits by ESEM imaging in the presence of a gaseous etch precursor and by pre-etching small features into a deposit (using a stationary or a scanned electron beam) prior to a final imaging process. The utility of this process is demonstrated by slimming of nanowires deposited by EBID, by the fabrication of gaps (between 4 and 7 nm wide) in the wires, and by the removal of thin films surrounding such nanowires. ESEM imaging provides a direct view of the slimming process, yielding process resolution that is limited by ESEM image resolution (~1 nm) and surface roughening occurring during etching. 2007 American Chemical Society.

We demonstrate a simple and effective approach for growing large-scale, high-density, and well-patterned conical boron nitride nanorods. A catalyst layer of Fe (NO3) 3 was patterned on a silicon substrate by using a copper grid as a mask. The nanorods were grown via annealing milled boron carbide powders at 1300 C in a flow of nitrogen gas. The as-grown nanorods exhibit uniform morphology and the catalyst pattern precisely defines the position of nanorod deposition. Cathodoluminescence (CL) spectra of the nanorods show two broad emission bands centered at 3.75 and 1.85 eV. Panchromatic CL images reveal clear patterned structure. 2006 American Institute of Physics.

Implantation with low-energy (80 keV) oxygen ions and subsequent rapid thermal annealing at 800 C are used to induce intermixing in a stack of 19 ZnO/Zn0.7Mg0.3O multiple quantum wells grown on sapphire by molecular beam epitaxy. Large blue shifts of more than 300 meV have been observed for doses up to 1 1016 cm-2, with no observation of saturation. This process is driven by the creation of defects by implantation which encourage the diffusion of Mg from the barrier layers into the ZnO quantum wells. Although defects are introduced during the implantation process, good recovery of the cathodoluminescence is seen following rapid thermal annealing. The Zn-Mg interdiffusion in this system has also been calculated for the corresponding ion doses, and the diffusion coefficient extracted. This study has significant implications for band gap engineering of ZnO/ZnMgO optoelectronic devices. 2006 IOP Publishing Ltd.

We present here the first high-resolution scanning tunneling microscope images showing that 1,4-phenylenedimethanethiol forms mono- and multilayers on gold(111) substrates under particular solution-deposition conditions. The high-resolution images show that the deposition conditions strongly influence the type of surface structure formed. The molecular structures were also probed using molecular-etching techniques and through deposition and imaging of gold nanoparticles. The current-voltage (I-V) characteristics of the multilayer structures are significantly different from those of monolayers. For the first time, scanning electron microscopy experiments were used to investigate the homogeneity of larger surface areas of the surface structures. 2006 American Chemical Society.

The influence of spherical nanoindentation on the band edge and deep level emission of single crystal c-axis ZnO has been studied by cathodoluminescence (CL) spectroscopy and monochromatic imaging. Excitonic emission is quenched at the indent site and defect emission in the range of 450-720 nm is enhanced. Analysis of CL monochromatic images and spectra suggests that at least two different defect states are responsible for the broad defect emission band. Additionally, the indents result in a strong crystallographic dependence of the defect emission, producing a rosette feature with [112?0] [21?1?0], and [12?10] orientations that reflect the star-shaped luminescence quenching observed at the excitonic peak (390 nm). 2006 American Institute of Physics.

Cathodoluminescence (CL) microscopy and spectroscopy are enabling techniques for the microcharacterisation of technologically important materials. Recent advances in SEM instrumentation have considerably expanded the microanalytical capabilities of the CL technique. In this paper, following a brief overview of the principles and practice of CL microscopy and spectroscopy, a number of examples are presented that demonstrate the utility of the technique for the microcharacterisation of advanced opto-electronic materials.

Zinc oxide (ZnO) nanoparticles have been produced using precipitation methods from ethanolic solution. Rare-earth metal doping was performed, and the effect of lithium codoping on the luminescence properties of the rare-earth doped products was assessed. The resulting particles were characterized using cathodoluminescence and scanning electron microscopy. It was found that lithium significantly enhanced the cathodoluminescence signal from the rare-earth ions, which has been attributed to the increased integration of the rare-earth ions into the ZnO structure. The nanophase ZnO products were also annealed in argon, hydrogen, and oxygen, with hydrogen being the most successful for removing the broad defect emission present in as-grown samples and enhancing the ZnO near band edge emission. Microscopy Society of America 2006.

Discolouring interactions between paint pigments have been observed since the mid 19th century. The source of some of these discolourations is the production of copper sulfides from an interaction between cadmium sulfide pigments and copper containing pigments. In this work, the discolouring interaction between cadmium yellow and malachite pigments was observed dynamically using the environmental scanning electron microscope (ESEM).

Cold pressed linseed oil and paints prepared using the inorganic pigments; lead white and red lead, were characterized using non-isothermal differential scanning calorimetry (DSC) in an air atmosphere to determine the effect of the pigment on the oxidative polymerisation of the drying oil medium. For each paint sample, the onset temperature for oxidation was reduced from 166C to the range 50 to 60C when a heating rate of 5 K min-1 was used. In order to determine the rate of drying, the non-isothermal experiments were carried out using a range of heating rates. A change in the mechanism oxidative polymerization was observed as the heating rate was increased. 2005 Akadmiai Kiad, Budapest.

We confirm changes to the band-gap of InN thin films treated in an electrochemical cell in which water electrolysis is evident. Electrical properties of the films were also affected. It is suggested that the change in the film resistivity results from hydrogen incorporation or removal during the electrolysis (dependent on sample polarity). The presence of grain boundaries is believed to enhance the penetration of chemical species into the InN resulting in a greater net change in the observed properties. 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

It is shown that the wide variation of apparent band-gap observed for thin films nominally referred to as InN is strongly influenced by variations in the nitrogen:indium stoichiometry. InN samples grown by remote plasma enhanced chemical vapour deposition show a change in band-gap between 1.8 and 1.0 eV that is not due to the Moss-Burstein effect, oxygen inclusion or quantum size effects, but for which changes in the growth temperature result in a strong change in stoichiometry. Material non-homogenity and non-stoichiometry appear to be general problems for InN growth. Excess nitrogen can be present at very high levels and indium rich material is also found. This work shows that the extent of the Moss-Burstein effect will have to be reassessed for InN. 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multilayer GaSb/GaAs quantum-dot (QD) structures grown by atmospheric-pressure metalorganic chemical vapor deposition on semi-insulating GaAs (100) substrates with varying growth temperature of the confinement layers are studied by the cathodoluminescence (CL). Two main features assigned to wetting layer and QDs are observed in the CL spectra. Their relative positions strongly depend on the growth conditions of the confinement layers. The highest separation of 270 meV is achieved for GaAs confinement layers grown at 540 C. 2005 American Institute of Physics.

Thin films of sphalerite-type ZnSe were grown by atomic layer deposition (ALD) from elemental Zn and Se precursors. These films, grown on various substrates, show bright blue `edge emission accompanied by donoracceptor pair emissions in the blue, green and red spectral regions. Red, green and blue emissions mixed together give a white color, with a color temperature between 2400 and 4500 K depending on a layer thickness and temperature. ZnSe grown by ALD is in consequence a promising material for the fabrication of semiconductor-based white light emitting thin film electroluminescence displays.

Cathodoluminescence (CL) and optical transmission spectroscopy were used to study the optical properties of molecular-beam-epitaxy (MBE) grown GaN with different doping levels. The 1-?m-thick samples were grown by plasma-induced MBE on c-plane Al 2O 3 substrate. The absorption measurements were performed at 2 K with a 250 W tungsten-halogen lamp. The CL measurements showed that Mn-doping concentrations around 10 20 cm -3 reduced the near band edge emission intensity by around one order of magnitude.

Scanning cathodoluminescence (CL) spectroscopy and imaging were used to study the effect of post-growth processing on the CL efficiency of metal-organic vapour phase epitaxy-grown Mg-doped GaN. In this work, two treatments, thermal annealing in high-purity gaseous atmospheres (N2, O2 and H2(5%)/N2) and low-energy electron beam irradiation (LEEBI), have been investigated. Post-growth annealing in a H2/N2 atmosphere followed by LEEBI leads to a significant enhancement of the free electron-to-bound Mg-acceptor (e, Mg) CL emission and a reduction of nonradiative centres involving native defects. The presented results demonstrate that the combination of post-growth annealing in a H2/N2 atmosphere and LEEBI dissociation of Mg-H complex acceptors significantly improves the light emitting efficiency of Mg-doped p-type GaN. Conversely, the samples annealed in a N2 or O2 atmosphere exhibit a reduced (e, Mg) emission after both annealing and LEEBI treatment.

Based on the results of optically detected magnetic resonance and time-resolved investigations we relate the observed lifetime shortening of intra-shell Mn2+ emission to spin dependent magnetic interactions between localized spins of Mn2+ ions and spins/magnetic moments of free carriers. We show that this mechanism is active in both bulk and in low dimensional structures, such as quantum wells, quantum dots, and nanostructures.

The mechanical deformation of wurtzite GaN epilayers grown on sapphire substrates is studied by spherical indentation, cross-sectional transmission electron microscopy (XTEM), and scanning cathodoluminescence (CL) monochromatic imaging. CL imaging of indents which exhibit plastic deformation (based on indentation data) shows an observable "footprint" of deformation-produced defects that result in a strong reduction in the intensity of CL emission. Multiple discontinuities are observed during loading when the maximum load is above the elastic-plastic threshold, and such a behavior can be correlated with multiple slip bands revealed by XTEM. No evidence of pressure-induced phase transformations is found from within the mechanically damaged regions using selected-area diffraction patterns. The main deformation mechanism appears to be the nucleation of slip on the basal planes, with dislocations being nucleated on additional planes on further loading. XTEM reveals no cracking or delamination in any of the samples studied for loads of up to 250 mN. 2002 American Institute of Physics.

Scanning and spot-mode cathodoluminescence investigations of homo- and hetero-epitaxial GaN films indicate a surprisingly small influence of their microstructure on overall intensity of a light emission. This we explain by a correlation between structural quality of these films and diffusion length of free carriers and excitons. Diffusion length increases with improving structural quality of the samples, which, in turn, enhances the rate of nonradiative recombination on structural defects, such as dislocations.

A simple method is described to determine the effective gas path length when incident electrons scatter in the gas above the specimen. This method is based on the measurement of a characteristic x-ray line emitted from a region close to the incident beam. From various experimental measurements performed on various microscopes, it is shown that the efefctive gas path length may increase with the chamber pressure and that it is also often dependent on the type of x-ray bullet.

Contact-induced damage has been studied in single-crystal (wurtzite) ZnO by cross-sectional transmission electron microscopy (XTEM) and scanning cathodoluminescence (CL) monochromatic imaging. XTEM reveals that the prime deformation mechanism in ZnO is the nucleation of slip on both the basal and pyramidal planes. Some indication of dislocation pinning was observed on the basal slip planes. No evidence of either a phase transformation or cracking was observed by XTEM in samples loaded up to 50 mN with an ?4.2 ?m radius spherical indenter. CL imaging reveals a quenching of near-gap emission by deformation-produced defects.Both XTEM and CL show that this comparatively soft material exhibits extensive deformation damage and that defects can propagate well beyond the deformed volume under contact. Results of this study have significant implications for the extent of contact-induced damage during fabrication of ZnO-based (opto)electronic devices. 2002 American Institute of Physics.

Cathodoluminescence (CL) spectroscopy shows that even relatively low-dose keV light-ion bombardment (corresponding to the generation of ?5 1019 vacancies/cm3) of wurtzite GaN results in a dramatic quenching of visible CL emission. Postimplantation annealing at temperatures up to 1050C generally causes a partial recovery of measured CL intensities. However, CL depth profiles indicate that, in most cases, such a recovery results from CL emission from virgin GaN, beyond the implanted layer due to a reduction in the extent of light absorption within the implanted layer. In this case, CL emission from the implanted layer remains completely quenched even after such an annealing. These results show that an understanding of the effects of ion bombardment and postimplantation annealing on luminescence generation and light absorption is required for a correct interpretation of luminescence spectra of GaN optically doped by keV ion implantation. 2001 American Institute of Physics.

A significant loss in electron probe current can occur before the electron beam enters the specimen chamber of an environmental scanning electron microscope (ESEM). This loss results from electron scattering in a gaseous jet formed inside and downstream (above) the pressure-limiting aperture (PLA), which separates the high-pressure and high-vacuum regions of the microscope. The electron beam loss above the PLA has been calculated for three different ESEMs, each with a different PLA geometry: an ElectroScan E3, a Philips XL30 ESEM, and a prototype instrument. The mass thickness of gas above the PLA in each case has been determined by Monte Carlo simulation of the gas density variation in the gas jet. It has been found that the PLA configurations used in the commercial instruments produce considerable loss in the electron probe current that dramatically degrades their performance at high chamber pressure and low accelerating voltage. These detrimental effects are minimized in the prototype instrument, which has an optimized thin-foil PLA design.

Optical emission spectra in the 300-700 nm range were collected from single crystal CaTiO3, SrTiO3 and BaTiO3, and polycrystalline CaTiO3 samples, that were irradiated at room temperature using a Febetron 706 variable energy pulsed-electron-beam generator. The long-lived emissions (up to microseconds after the electron pulse) consist of broad (halfwidths to approximately 100 nm) bands centred around 380, 425, and 445 nm for CaTiO3, SrTiO3 and BaTiO3, respectively. These emission bands are similar to cathodoluminescence emissions from 25 keV electron irradiation attributed by others to direct conduction-valence band transitions in unreduced samples and oxygen vacancies in reduced samples. CaTiO3, SrTiO3 and BaTiO3 all have emission thresholds of 0.260.02 MeV. This corresponds to a threshold displacement energy for oxygen, Ed of 454 eV.

We present direct experimental evidence for a field assisted component in images acquired using the gaseous secondary electron detector (GSED) employed in environmental scanning electron microscopes. Enhanced secondary electron (SE) emission was observed in GSED images of epitaxial GaN bombarded with MeV He ions. The increase in SE emission is attributed to an electric field generated by electrons trapped at defects produced by ion implantation. The presence of nonradiative recombination centers and of trapped charge in implanted GaN was established by cathodoluminescence spectroscopy and energy dispersive x-ray spectrometry. The field assisted SE component is distinguishable from the "normal" GSED signal by characteristic pressure and temperature dependencies. The presented results demonstrate the utility of the GSED for imaging charge trap distributions in semiconductors. 2000 American Institute of Physics.

Cathodoluminescence has recently been used successfully in detecting and determining the spatial location of the amorphous phase in plasma sprayed calcium phosphate coatings. The aim of this study is to determine whether this same technique can be used t

The differential absorption of a GaAs single quantum well is studied for resonant pumping at either the heavy- or light-hole exciton resonances using different polarization configurations. For all excitation conditions the observed spectra show bleaching

Trace levels of Cr impurities in epitaxial GaN grown on sapphire substrates were investigated using cathodoluminescence (CL) spectroscopy. CL emissions characteristic of Cr in an octahedral crystal field were observed from ?-Ga2O3 overlayers produced on GaN by post-growth thermal annealing in dry O2. Cr luminescence was also observed from the sapphire substrates, a likely source of the Cr contaminant. The presented results illustrate the use of ?-Ga2O3 overlayers as high sensitivity indicators of the presence of Cr in GaN. 1999 American Institute of Physics.

A new type of quantum dot (QD) alignment for an InGaAs/GaAs QD multilayered structure has been observed. In addition to two distinct types of InGaAs dot alignment in vicinal GaAs (001), an abrupt transition in QD sizes and concentrations was seen. This was accompanied by bright QD emission, even after formation of a dislocation array, and different behaviors with thermal intermixing.

We report the observation of quantum beat-like oscillations in transient four-wave mixing (FWM) of heavy-hole and light-hole excitonic transitions that share no common upper or lower states. Theoretical analysis shows that these oscillations arise from p

We present experimental evidence of electron-beam-induced diffusion of O and H in unintentionally doped n-type GaN grown on a sapphire substrate. Impurity diffusion was investigated using cathodoluminescence kinetics and imaging at 4 and 300 K and by wavelength dispersive x-ray analysis. The results illustrate the significance of electron-beam-induced electromigration in wide band gap semiconductors, confirm the roles of ON. in bound exciton, donor-acceptor pair and yellow emissions and suggest the involvement of ON. and hydrogenated gallium vacancies in the previously unexplained blue luminescence. 1999 The American Physical Society.

The presence and distribution of the amorphous phase is a key factor in the performance and bone-bonding behavior of plasma-sprayed hydroxyapatite coatings. Microanalysis of coatings was conducted with microprobe Raman and scanning cathodoluminescence microscopy. It was confirmed that the darker regions in polished cross sections represent the amorphous phase. The more intense cathodoluminescence emission from the amorphous phase during electron-beam irradiation compared with the crystalline phase was used to detect the two structurally different areas within the sample. By selecting the peak of the emission at 450 nm it was possible to raster the surface with the electron beam and produce a map of the amorphous phase in polished sections, a fracture surface and an as-sprayed surface of the plasma-sprayed coating. Cathodoluminescence microscopy, based on the different light emission from the amorphous phase and hydroxyapatite, is a useful tool for identifying and mapping of the amorphous-phase constituent in plasma-sprayed coatings.

This work demonstrates the validity of approximating cathodoluminescence generation throughout the electron interaction volume by the total electron energy loss profile. The energy loss profiles in multilayer specimens were accurately calculated using the Monte Carlo simulation CASINO. Resolution of cathodoluminescence images can be estimated from the electron beam spot diameter, the electron penetration range, and the minority carrier diffusion length.

The irradiation of crystalline (?-SiO2) and amorphous (?-SiO2) silicon dioxide with a stationary electron beam produces characteristic changes in the surface topography. The development of these changes has been investigated using cathodoluminescence spectroscopy and microscopy, scanning probe (atomic force) microscopy, and scanning electron microscopy. Electron irradiation produces a permanent volume increase on (crystalline) ?-SiO2, while in (amorphous) ?-SiO2 an initial small volume increase is followed by volume loss as irradiation continues. The observed changes are consistent with electromigration of oxygen under the influence of the electric field induced by charge trapping at preexisting or irradiation-induced defects. Oxygen enrichment may produce expansion of the surface region due to the formation of peroxy linkage defects. In ?-SiO2, charges trapped by defects at grain boundaries produce enhanced electric fields which may result in volume reduction at the surface, when critical field strengths are exceeded. The observed volume reductions may be attributed to electron stimulated desorption of constituents, in particular oxygen mass loss, and densification of the surface region associated with the formation of oxygen-deficient defect centers. 1996 American Institute of Physics.

Effects of anodic oxide induced intermixing on the structural and optical properties of stacked GaAs quantum wire (QWR) structures grown on a sawtooth-type nonplanar GaAs substrate are investigated. Cross-sectional transmission electron microscope (XTEM) observation, temperature dependent photoluminescence (PL) and cathodoluminescence (CL) imaging were used. Intermixing was achieved by pulsed anodic oxidation of the GaAs cap layer and subsequent rapid thermal annealing, was verified by XTEM analysis. A significant enhancement of QWR PL is observed accompanied by a notable blueshift of the sidewall quantum well (SQWL) PL due to the intermixing. Furthermore, an extended necking region is observed after the intermixing by spatially resolved CL. The temperature dependence of the PL intensities of both SQWL and QWR show maxima at approximately T ?110 K indicating the role of the extended necking region in feeding carriers to SQWL and QWR. 1996 American Institute of Physics.

The irradiation of natural and ultrapure synthetic crystalline quartz by a stationary electron beam produces surface outgrowths, which have been analyzed using scanning electron microscopy, atomic force microscopy, cathodoluminescence spectroscopy, and microscopy. Oxygen enrichment of the quartz surface occurs due to electromigration resulting from the trapped charge induced electric field. It is proposed that the accumulated oxygen is incorporated into the quartz surface structure as peroxy linkages, the formation of which results in the permanent volume increase observed as amorphous outgrowths on crystalline quartz. A cathodoluminescence emission at 2.3 eV localized on the outgrowths, is attributed to an intrinsic process. 1995 American Institute of Physics.

Spatially resolved cathodoluminescence (CL) spectra were measured on porous silicon. The CL spectra showed bands and prominent peaks ranging in energy between 1.45 eV and 3 eV and were unlike the photoluminescence spectra measured on the same samples, wh

Titania, TiO2, precipitation in natural blue sapphire (Fe, Ti: ?-Al2O3) has been investigated using high resolution and analytical transmission electron microscopy. The structure and habit of the TiO2 precipitate depends on both the Ti4+ concentration and the temperature at which the precipitate formed. Tetragonal TiO2 (Rutile) grows at 1350 C but at 1150 C an orthorhombic non-equilibrium TiO2 polymorph precipitates. Both TiO2 polymorphs nucleate in the (0001)s plane as lens shaped discs twinned along their diameter. The crystallographic alignment of each type of TiO2 precipitate with respect to the ?-Al2O3 host matrix provides a high degree of structural coherency with minimal lattice mismatch. Electron diffraction analysis established the following precipitate/host orientation relationships: tetragonal TiO2: {011}r{norm of matrix} {11 {Mathematical expression}07B;100}r{norm of matrix}(0001)s and ?01 {Mathematical expression}?r?10 {Mathematical expression}0?s twinned along the (011)r planeand orthorhombic TiO2: {021}?{norm of matrix}{11 {Mathematical expression}0}s, {100}?{norm of matrix}(0001)s and ?0 {Mathematical expression}2? ?{norm of matrix}?10 {Mathematical expression}0?s twinned along the (021)? plane. 1991 Springer-Verlag.

A simple and inexpensive ''feedback'' circuit has been devised that regulates the gas flow in an argon ion gun system and thus optimizes the specimen thinning rate. The circuit is easily adapted to suit a broad range of similar applications.

In order to investigate the defect structure of Ti:?-Al2O3, protons were incorporated into aluminium oxide single crystals doped with tetravalent titanium. This produced a set of sharp bands in the i.r. spectrum with stretching frequencies around 3300 cm-1, characteristic of OH bands. The thermal behaviour of these bands was investigated in a series of isochronal and isothermal heating experiments, monitored using FTIR spectroscopy. The i.r. spectra consisted of three main absorption bands at 3309cm-1, 3232cm-1 and 3187cm-1. The i.r. band at 3309cm-1 has been assigned to a (Ti.AlV'''AlOH.oTi.Al)x defect cluster. The lower energy bands at 3232cm-1 and 3187cm-1 were assigned to two structural variants of a (Ti.AlV'''AlOH.o)' defect cluster. The (Ti.AlV'''AlOH.oTi.Al)x defect cluster forms via the following reversible internal diffusion-limited association reaction Ti.Al + (Ti.AlV'''AlOH.o)' ? (Ti.AlV'''AlOH.o)x. The binding enthalpy for this reaction was determined to be 1.06 0.20 eV. The clustering reaction was observed to follow first order reaction kinetics. An activation energy of 2.5 0.1 eV was determined for the (Ti.AlV'''AlOH.o)' cluster. The relative concentration of all charged and neutral defect associates was found to critically depend on the thermal history of the crystal. The defect structure of Ti4+:?-Al2O3 is also discussed with reference to this study. 1991.